Multi-functional lubricant addition agents and lubricants containing same



United States Patent Office 3, 1 6'9 9814 Patented Nov. 5, 1 963 3,109,814 MULTI-FUNCTIONAL LUBRICANT ADDITIQN zslGENTs AND LUBEJCANTS CONTAINING AME Albert R. Sahel, Munster, and Eli W. Blaha, Highland, Ind, and Ray Edward Koskie, Chicago Heights, liL, assignors to Standard Oil Company, Chicago, Ill., a corporation of Indiana No Drawing. Fiied Jan. 11, 1960, Ser. No. 1,412

, 7 Claims. (Ql. 25232.7)

This invention relates to novel compositions of matter which are effective as multi-functional addition agents in lubricant compositions. More particularly, this invention pertains to improved lubricant compositions containing novel oil-soluble neutralized phosphorus sulfide-hydrocarbon reaction products complexed with boric acid having a high metal to phosphorus content ratio and being capable of improving the detergency, rust inhibition, anti-wear, bearing corrosion inhibition, and oxidation inhibition of the lubricating oil.

Within recent years it has become common practice to impart improved properties to lubricants through the use of various types of addition agents. Lubricating oils employed in internal combustion engines, such as spark ignition and diesel engines, generally require the use of many varied addition agents to improve the serviceability of the lubricating oil under the conditions of operation of the engine. Because the conditions of operation of an engine are such as to require such improvement in serviceability of a lubricating oil, many different types of additives are employed. Among the more important additives employed, is the type which functions to prevent the formation and accumulation of sludge and varnish deposits and coatings on cylinder and piston walls of engines. Such addition agents have the property of maintaining clean engines and are referred to as detergenttype addition agents. Such detergent-type addition agents generally must be effective under the heavy duty, high temperature'conditions of modern engine operation; it is desirable to provide satisfactory detergency addition agents for such conditions. Another desirable addition agent in common usage is the rust inhibitor. The rust inhibitor functions to prevent the adverse oxidation and rusting of metallic parts, particularly those parts containing ferrous metals. In addition, anti-wear addition agents are useful in preventing undue Wear of moving parts under severe operating conditions; bearing corrosion inhibitors are useful in inhibiting corrosion to alloy bearings and other alloy metal parts in contact with the lubricating oil which bearings and metal parts are susceptible to corrosion by acidic materials, such as chlorides and sulfates; oxidation inhibitors" are useful in inhibiting the formation of sludge caused by oxidation of the lubricating oil itself.

In modern internal combustion engines, it is necessary to use many varied addition agents to accomplish the many varied desired results as indicated above. In recent years, multi-purpose addition agents have been considered as an answer to engine lubrication problems because use of such multi-purpose or multi-functional agents reduces the number and amounts of addition agents required.

Also in recent years, the use of neutralized phosphorus sulfide hydrocarbon reaction products as lubricant addition agents has become more and more prominent. When neutralizing such products, with barium, in processes for preparing such addition agents, many problems in handling the reactants and reaction product have been incurred. Often in such neutralizations, the product is difficult to filter and has a hazy appearance, detracting from its commercial acceptability.

We have provided certain new and useful oil-soluble neutralized phosphorus sulfide-hydrocarbon reaction product complexes for use as multi-purpose addition agents in lubricants. The addition agents of this invention are easily filtered and clear in appearance and are useful as multi-purpose addition agents in lubricating oils in amounts from about .002 to about 15 weight percent for the purpose of imparting detergency, rust inhibition, anti-wear properties, bearing corrosion inhibition, and oxidation inhibition. The process for their preparation eliminates hazy appearance in the final product. The additive complexes of this invention are formed by partially neutralizing an unhydrolyzed phosphorus sulfidehydrocarbon reaction product with a basic zinc compound such as, for example zinc oxide, in the presence of boric acid and an alcohol reaction solvent. After partial neutralization of the reaction product and boric acid mixture with the basic zinc compound, the mixture is further reacted with an excess of an inorganic basic metal compound selected from basic alkali and alkaline earth metal compounds, such as, for example, barium oxide, to impart high metal content thereto.

The alcohol reaction solvent may be any aliphatic alcohol boiling below about 350 F. or mixture of such alcohol with water. More advantageously the aliphatic alcohol is a saturated aliphatic alcohol having from 1 to about 7 carbon atoms. Methanol is particularly preferred. Where a mixture of alcohol and Water is used as the alcohol reaction solvent, the Water may be present in amounts up to about 2.0 mols, advantageously at least about .05 mol, and preferably from about 0.5 mol to about 1.5 mols per mol of basic alkali or alkaline earth compound. Examples of suitable aliphatic alcohols are methanol, ethanol, isopropanol, butanol, pentenol, pentanol, methyl-butyl alcohol, hexanol, ethyl-hexyl alcohol, octyl alcohol, and the like. The alcohol reaction solvent is used during the above partial neutralization with basic zinc compound and further reaction with excess inorganic basic alkali or alkaline earth metal compound in amounts sufiicient to provide from about 2 to about 15 mols of aliphatic alcohol per mol of inorganic basic metal compoundand preferably from about 3 to about 7 mols per mol of inorganic basic alkali or alkaline earth metal compound.

The partial neutralization step is carried out by reacting the basic zinc compound with the phosphorus sulfidehydrocarbon reaction product in the presence of a boric acid compound and the reaction solvent in admixture at a temperature in a range from about F. to about 400 F. and preferably from about F. to about 200 F. It is advantageous to carry the reaction out at the reflux temperature of the aliphatic alcohol reaction solvent since the reaction temperature can thereby be more easily controlled. The reaction with the basic zinc compound forms a partially neutralized product having zinc and phosphorus present in about equal molecular amounts. It is preferred to use from about .5 to about 1.6 mols of basic zinc compound per mol of phosphorus in the phosphorus sulfide-hydrocarbon reaction product in the reaction mixture although any amount of from about .3 to about 4.0 or more mols of basic zinc compound per mol of phosphorus may be used. Hereinafter, the basic zinc compound will be referred to as zinc oxide, although it is to be understood that in addition to zinc oxide, other inorganic basic zinc compounds such as zinc carbonate, zinc sulfate, zinc phosphate, zinc sulfide, or the like may be used and all such basic zinc compounds are intended herein wherever zinc oxide is mentioned.

During the partial neutralization with zinc oxide and the subsequent reaction with the excess inorganic basic alkali or alkaline earth metal compound, in the preferred embodiment of this invention, a polymerization product of an unsaturated fatty acid, i.e.'a polymerized fatty acid, is also included in the reaction mixture in amounts from about .1 to mols and preferably from about .2 to about 6.0 mols per molecule of phosphorus in the phosphorus sulfide-hydrocarbon reaction product.

After the partial neutralization with zinc oxide, the resulting partially neutralized reaction product is reacted with at least about 0.5 and up to about 2 or more mols of an inorganic basic alkali or alkaline earth metal compound per mole of phosphorus in the reaction product. The reaction is carried out at a temperature in the range of from about 120 F. to about 400 F. and preferably from about 140 F. to about 200 F. Again the reaction is advantageously carried out at the reflux temperature of the aliphatic alcohol reaction solvent. Hereinafter, the inorganic basic alkali or alkaline earth metal compound will be referred to for convenience as barium oxide, the preferred compound, although it is to be understood that in addition to barium om'de, other inorganic basic barium compounds, for example, the inorganic basic salts of the alkali metals and alkaline earth metals, such as the oxides, hydroxides, sulfides, carbonates, etc. of sodium, potassium, lithium, calcium, barium, etc. may be used and all such inorganic basic alkali or alkaline earth metal compounds are intended hereinafter wherever barium oxide is mentioned. More specific examples of such compounds are sodium carbonate, sodium bicarbonatqsodium hydroxide, sodium sulfide, potassium hydroxide, lithium bron1ide, potassium carbonate, calcium oxide, calcium carbonate, calcium sulfide, calcium hydroxide, strontium oxide, barium oxide, barium hydroxide, barium sulfide, barium carbonate, etc.

The basic barium compounds are most advantageous.

In the preferred process of this invention, the basic alkali or alkaline earth metal compound is added to the mixture of reactants following the partial neutralization with :basic'zinc compound without cooling the zinc neutralized product. The basic alkali or alkaline earth metal compound reaction is carried out in the presence of the aliphatic alcohol reaction solvent and the boric acid compound.

The polymerized fatty acid, when included in the reaction mixture during partial neutralization with zinc oxide, is present during the barium reaction and becomes part of the complex formed. The polymerized fatty acid present as part of the complex imparts further improved properties to the addition agents of this invention particularly with regard to rust inhibition. Where the polymerized fatty acid has been included in the reaction mixture during the partial neutralization with basic zinc compound, then in the reaction with basic alkali or alkaline earth metal compound it is more advantageous to use a greater amount of such basic metal compound based on phosphorus sulfidehydrocarbon reaction product and preferably from about 1.1 to about 1.4 mols basic alkali or alkaline earth metal compound per mol of phosphorus in the reaction product. However, where no polymerized fatty acid has been included in the zinc reaction, then in the alkali or alkaline earth metal reaction it is preferred to use from about 0.9 to about 1.4 mols alkali or alkaline earth compound per mol of phosphorus in the phosphorus sulfide-hydrocarbon reaction product.

After the reaction with the alkali or alkaline earth metal compound, the resulting product is filtered to remove solid materials such as inorganic zinc and alkali or alkaline earth metal salts; filtration may be easily accomplished by diluting the product with mineral lubricating oil and heating the diluted product to a temperature in the range of from about 200 to about 400 F. and preferably about 350 F. and then filtering the heated diluted product through an absorbent material such as silica gel, Celite, Attapulgus clay, fullers earth, or the like.

In accordance with a particular procedure of this invention, the aliphatic alcohol reaction solvent and the boric acidcompound (and the polymerized fatty acid, if used) may be heated to reaction temperature before addition of the basic zinc compound for partial neutralization. Other embodiments Will be obvious to those skilled in the art. However, in any embodiment, the partial neutralization of the reaction mixture with the basic zinc compound must be allowed to go to substantial completion before addition of the basic alkali or alkaline earth compound in order to obtain acceptable addition agents in accordance with this invention. I

The phosphorus sulfide-hydrocarbon reaction product may be prepared by reacting a normally liquid hydocarbon with a phosphorus sulfide, such as P 8 P 8 P 5 or other phosphorus sulfides, and preferably phosphorus pentasulfide, P 8

The normally liquid hydrocarbon constituent of this reaction is suitably a high boiling hydrocarbon such as is described in detail in US. 2,316,080, 2,316,082, and 2,316,088, each issued to Loane et al. on April 6, 1943. While the hydrocarbon constituent of this reaction can be any of the type hereinafter described, it is preferred a mono-olefin hydrocarbon polymer resulting from the polymerization of lower molecular Weight mono-olefinic hydrocarbons or isomono-olefinic hydrocarbons, such as butylenes, or the copolymers obtained by the polymerization of hydrocarbon mixtures containing isomono-olefins rand mono-olefins or mixtures of olefins in the presence of a catalyst, such as sulfuric acid, phosphoric acid, boron fluoride, aluminum chloride or other similar halide catalysts of the Friedel-Crafts type.

The polymers employed are preferably (mono-olefin polymers .ormixtures of mono-olefin polymers and isomono-olefin polymers having molecular weights ranging from about 150 to about 50,000 or more, and preferably from about 300 to about 10,000. Such polymers can be obtained, for example, by the polymerization in the liquid phase of a hydrocarbon mixture containing mono-olefins and isomono-olefins such as butylene and isobutylene at atemperature of from about -80 to about 100 F. in the presence of a metal halide catalyst of the Friedel- Crafts types such as, for example, boron fluoride, aluminum chloride, and the like. In the preparation of these polymers we may employ, for example, a hydrocarbon mixture containing isobutylene, butylenes and butanes recovered from petroleum gases, especially those gases produced in the cracking of petroleum oils in the manufacture of gasoline.

Essentially parafiinic hydrocarbons such as bright stock residuurns, lubricating oil distillates, petroleum, or paraffin Waxes, may be used. There can also be employed the condensation products of any of the foregoing hydrocarbons, usually through first halogen-ating the hydrocarbons, with aromatic hydrocarbons in the presence of anhydrous inorganic halides, such as aluminum chloride, zinc chloride, boron fluoride, and the like.

Other preferred olefins suitable for the preparation of the herein described phosphorus sulfide reaction products are olefins having at least 20* carbon atoms in the molecule of which from about 13 carbon atoms to about 18 carbon atoms, and preferably at' least 15 carbon atoms, are in a long chain. genation of paraffins, such as by the cracking of paraffin Waxes or by the dehalogenation of alkyl halides, preferably long chain alkyl halides, particularly halogenated paraffin waxes. I

The phosphorus sulfide-hydrocarbon reaction product is prepared by reacting the phosphorus sulfide, e.g. P 8 with the hydrocarbon at a temperature of from about F. to about 600 F., preferably from about 300 F. to about 500 F., using from 1% to about 50%, preferably from about 5% to about 25% of phosphorus sulfide; the reaction is carried out in from one to about ten hours. It is preferable to' use an amount of the phosphorus sul- Such olefins can be obtained by the dehydrofide that will completely react with the hydrocarbon so that no further purification is necessary; however, an excess of the phosphorus sulfide can be used, and the un reacted material separated by filtration. The reaction, is desired, can be carried out in the presence of a sulfurizing agent such as sulfur or a halide of sulfur as described in US. 2,316,087 issued to J. W. Gaynor et a1. April 6, 1943. It is advantageous to maintain a nonoxidizing atmosphere, for example an atmosphere of nitrogen, in the reaction vessel. Under the above conditions, hydrolysis of the reaction product does not occur.

The boric acid is added to the neutralization reaction in amounts of from about 0.1 to about 5.0 mols and preferably from about 0.5 to about 2.5 mols per mol of phosphorus in the phosphorus sulfide-hydrocarbon reaction product. The boric acid can be added as boric acid or can be prepared in situ in the reaction mixture by adding boric acid anhydride or a boric acid ester which is capable of decomposition to give boric acid in the reaction mixture, for example, by dissociation upon heating.

The polymerized fatty acids or polymerized products of the unsaturated fatty acids are those such as may be ob tained by the polymerization of natural or synthetic monocarboxylic acids which generally will have 16 to 26 carbon atoms, most frequently 18 carbon atoms, but if syn thetic unsaturated fatty acids are used they may have a lesser or greater number of carbon atoms. Examples of the natural fatty acids are those such as linoleic, linolenic, ricinoleic (winch upon heating forms linoleic acid), linoleaidic, elaidolinolenic, eleostearic, arachidonic, eicosatrienoic, cetoleic, decosatrienoic and the like. The free fatty acids can be polymerized either thermally or with the assistance of catalysts. A method of thermally polymerizing free fatty acids (see US. 2,482,761) consists of hydrolyzing a fat or an oil, adding a small portion of water, and heating in a pressure vessel until substantially all of the diand tri-unsaturated fatty acids present polymerize. The resultant product is then heated at a re duced pressure to distil off vaporizable constituents, leaving behind the polymerized unsaturated fatty acids. The polymerization reaction is carried out at a temperature of about 300 to 360 C. for about 3 to 8 hours at a pressure varying between 75 and 500 p.s.i.g. The polymerization product may consist of monomers, dimers, trimers, and higher polymers of the unsaturated fatty acids. The various fats or oils which may be hydrolyzed to produce the free fatty acids used in the above thermal polymerization are those such as sardine oil, linseed oil, soybean oil, castor oil, peanut oil, palm oil, olive oil, cottonseed oil, sunflower seed oil, and the like.

Another method of preparing the polymerized fatty acids consists of subjecting fats and oils such as have been listed supra (without previous hydrolysis) to a thermal or catalytic polymerization to cause polymerization of the esters of the unsaturated carboxylic acids to the dimers, trimers, and higher polymerization products thereof followed by hydrolysis to yield the corresponding polymers of the acids. A large source of the polymerized unsaturated fatty acids are those residual acids obtained by methanolysis (see US. 2,450,940) of the semi-drying or drying type oils such as castor oil, soybean oil, and others listed supra, polymerizing the methyl esters, removing unpolymerized compounds, saponifying the residual esters and freeing polymerized acids therefrom. The products of catalytic polymerization of semi-drying oils such as the BF polymerization products of soybean oil, cottonseed oil, or the like also produce polymers suitable for use in the invention.

It should be understood that while various polymerized unsaturated fatty acids may be used, they do not all provide the same effect, and indeed there may be pronounced differences when used in the composition of this invention. A highly preferred source of the polymerized unsaturated fatty acids is obtained as a by-product still rescomprises monomers, dimers, trimers and higher poly-- mers in the ratio of from about 45 to about 55% of a monomers and dimers fraction having a molecular weight in the range of from about 300 to 600 and from about 45 to about 55% of a trimers and higher polymer frac tion having a molecular weight in excess of 600. The fatty acid polymers result in part from a thermal polymerization of fatty acid type constituents of the castor oil, and in part from other reactions such as the inter-molecular esterification of such acid to form high. molecular weight products. The acid mixture, which is mainly a mixture of polymeric long chain poly-basis carboxylic acids, is further characterized by the following specifications:

Acid No to 164 Saponification No to 186 Free fatty acids percent 75 to 82 Iodine value 44 to 55 Non-saponifiables percent 2.5 to 5 A fatty acid mixture such as above described is marketed under the trade name Hardestey D50 Acids and also as VR-l Acids.

The polymerization products of the unsaturated fatty acids may have a molecular weight between about 400 and 2000. Those polymers having a molecular weight higher than about 500, and especially those having molecular Weight averaging about 800 or higher are particularly preferred for use in this invention. The polymerization products may consist primarly of dimers and trimers of linoleic acid, for example Emery 955 dimer acid Which contains 85% of the dimer, 12% of the trimer, and 3% of the monomer of linoleic acid may be used. Especially preferred polymerized unsaturated acids are the polymerization products of acids such as linoleic acid having a molecular weight between about 300 and 2000, wherein the polymerization products consist of from about 45% to about 5 5% of monomers and dimers fraction of linoleic acid having a molecular weight ranging from 300 to 600 and from about 45% to about 55 of the trimer and higher molecular weight polymers fraction of linoleic acid having a molecular weight in excess of about 600.

Although we do not wish to be held to any theories regarding the reaction, we believe that the addition of boric acid and polymerized fatty acid to the barium neutralization reaction mixture causes a complex of such components with the phosphorus sulfide-hydrocarbon reaction product to form. The complex, in turn, reacts with excess barium oxide to form the lubricant addition agents of this invention.

The following examples are included as illustrations of the preparation of reaction products of this invention and are not intended as limiting our invention.

PREPARATION: UN HYDROLYZED PHOSPHORUS SULFIDE-HYDROCARBON REACTION PRODUCT As an illustration of the preparation of the unhydrolyzed phosphorus sulfide-hydrocarbon reaction product used an intermediate in the preparation of addition agents of this invention, a butene polymer'having an average molecular weight in the range of about 750 to 800 was reacted with 15.5 weight percent P 8 at a temperature of about 450 F. for a period of about 5.5 hours. The resulting product was diluted with SAE 5 mineral lubricating oil to a phosphorus content of about 31 grams per 1200 grams of diluted product.

Y Example I As an illustration of the preparation of an addition agent in accordance herewith, 1200 grams of the phosphorus sulfide-polybutene reaction product of the above with 320 grams of SAE mineral lubricating oil and heated to a temperature of 160 F. (reflux temperature) and maintained at that temperature for about 1 hour. 240 grams of barium oxide were then added to the reaction mixture and heating at about 160 F. was continued for 2 hours. The product was then heated to about 300 F. and filtered through Celite. The filtered product contained 6.5% barium, 0.93% zinc, 1.1% phosphorus, 2.21% sulfur, and 0.31% boron.

In accordance with the procedure of Example I, satisfactory products may be prepared, as further illustrations of this invention by substituting molar equivalents of lithium hydroxide, sodium carbonate, potassium sulfide, or calcium oxide, for example, for the barium oxide used above. 1

Example II In order todemonstrate the preparation of the compositions of this invention wherein the zinc oxide is added to partially neutralize the phosphorus sulfide-hydrocarbon reaction product and boric acid after heating the latter components to reaction temperature, the following procedure was carried out: 1200 grams of a P S -polybutene reaction product prepared as in the above preparation and 60 grams of boric acid (per mole of phosphorus in the reaction product) were dissolved in 500 ml. of

methanol and heated at a temperature of ISO-160 F.

(methanol reflux temperature) for 2 hours. 40 grams of zinc oxide were added to the heated mixture and the resulting mixture was heated at the reflux temperature of methanol (about 160 F.) for 2 hours. 240 grams of barium oxide were then added to the resulting partially Example 111 As an example of the preparation of a preferred composition of this invention in the presence of a polymerized fatty acid, 880 grams of the phosphorus sulfide polybutene reaction product of the above preparation, 640 grams of a solvent extracted SAE 5 mineral lubricating oil, 62 grams of Hardesty D-50 acid (described above) and 62 grams of boric acid were mixed with 500 cc. of methanol and 22 cc. of water and heated for 1 hour at the reflux temperature of the methanol and water mixture (about 160 F.) 40 grams of zinc oxide were added to the reaction mixture and heating at reflux tem perature was continued for 2 hours to assure neutralization. The partially neutralized product was further reacted with 230 grams of barium oxide added as a slurry in 400 grams of Mid-Continent solvent extracted mineral 8 7 ing oils, the samples listed below were subjected to the Oldsmobile M.S. Test Sequence 1, II, and III, designed by General Motors Research Division. The Oldsmobile sequence evaluates detergency, rust inhibition, valve lifter corrosion inhibition, anti-wear and oxidation inhibition of lubricating oils tested. Briefly the test consists of using the sample to be tested as a lubricating oil in an Oldsmobile V-8 engine (1958) under the following conditions in a complete test from sequence I through sequence 1111.

Sequence I.-The engine is run under the following conditions Speedu' 2500120 r.p.m. Load No load. Coolant out temp 95::20 F.

Oil sump temp 120 F. max. Crankcase ventilation Cork in breather.

Humidity (Dew Call Chart) 75-85 grains per pound.

Speed 1500:30 rpm. Load (25 HP.) 67:2#. Coolant out temp 95i2 F.

Oil sump temp 120:2 F.

Crankcase ventilation Cork in breather. Humidity 75-85 grains per'pound.

Sequence II is also conducted on cyclic operation, each cycle constituting 3 hours running the above conditions and 3 hours ofP while maintaining the specified coolant out temperature, for a total of 16 cycles.

At the end of sequence II, one valve lifter is removed and inspected for evidence of rusting .If no excessive rusting or corrosion is observed the test is continued to sequence III.

Sequence lII.-The engine is run continuously for 36 hours under the following conditions:

Speed 3400:20 r.p.m.

Load (85 H.P.)'100:2#. Coolant out temp 200i2 F. 7 Oil sump temp 265i2 F.

Crankcase ventilation Normal breather cap on. Humidity 75-85 grains per pound.

Samples of oil, /2 pint each, may be taken during the above procedure at various intervals of operation and on oil at refiux temperature for 2 hours. The reaction mixture was then heated to 350 F. and filtered through Celite. The filtered product contained 1.33% zinc, 1.32%

phosphorus, 8.14% barium, and 0.34 boron. The prodcompletion of the test.v Such samples may be subjected to tests and analyses as desired. The oil is checked at the end of sequence I and after each sampling. Fresh oil is added to the 5 quart mark after each oil check, but the oil is not changed throughout the series'of tests.

On completion of the above three sequences without oil drain and without oil consumption exceeding 5 quarts, the engine is completely disassembled and inspected for scufiing, wear, rusting, corrosion and sludge and varnish deposition.

The following samples were tested in accordance with the above procedure:

Sample A.-A solvent extracted Mid-Continent SAE 10 mineral lubricating oil containing 6.0 weight percent of Example I. 7

Sample B.--A- solvent extracted Mid-Continent SAE 10 mineral lubricating oil containing 5.2. weight percent of Example III.

The results of testing the above samples are recorded below. Following the reported results are the requirements for passing the test.

(a) with from about 0.5 to about 2.5 moles of boric acid per mole of phosphorous in said reaction product,

Sample A S ample B Requirements Lifter Condition at End of Can Scutting Phase Sl. Scufiing, 1 Lifter N Scuffimz No Seuflng. Average Cam and Lifter Wear .0009 in .0007 in Less than .0040 in. Maximum Total Cam and Mating Lifter Wear. .0017 in .0008 in Less than .0060 in. Rust on Valve Lifter Bodies 1 Clean Clean (l0) At least 6.0 Rust on Valve Lifter Plungers S1. Rust Clean (10) At least 6.0 Average Rust 1 including Piston Pins, Valve Stems,

Push Rods, Cylinder Walls and Oil Pump Relief Valve Clean (about 9.0).... At least 7.0 Connecting Rod Copper-Lead Bearings, wt. Loss per Bearin 38.6 m Less than 200 mg. Ring Stickin None None None Plugging of Oil Control Rin s None N one None Top Engine Cover Sludge 9.4.. 10.0 At least 8.0 Average Sludge 2 including Rocker Arm Cover, Oil Pan,

Rocker Arm Assembly, and Oil Screen 9.4-. 10.0.- At least 8.5 Piston Varnish 9.7. 10.0 At least 9.0 Average Varnish 2 including Rocker Arm Cover, Cylinder Bore, Oil Pan, and Top Engine Cover 9.5 9.9.. At least 9.0

1 General Motors Rust Rating Scale. 2 CRC Deposit Scale.

The results from the Oldsmobile engine test, above, demonstrate the detergency, rust inhibitor, anti-wear, corrosion inhibition, and oxidation inhibition properties of lubricating oils containing the addition agents of this invention.

The herein described additive compositions of the present invention can be used as indicated above in varying amounts of from .002 up to about in lubricating oils. Although the present invention has been illustrated by the use of the additive compositions in mineral lubricating oils, it is not restricted thereto. Other lubricating oil bases can be used, such as hydrocarbon oils, both natural and synthetic for example, those obtained by the polymerization of olefins, as well as synthetic lubricating oils of the alkylene oxide type and the polycarboxylic acid ester type, such as the oil soluble esters of adipic acid, sebacic acid, azelaic acid, etc. It is also contemplated that various other well known additives, such as antioxidants, anti-foaming agents pourpoint depressors, extreme pressure agents, anti-wear agents, may be incorporated in lubricating oils containing the additives of our invention.

Concentrates of a suitable oil base containing more than 15 percent, for example up to 50 percent or more, of the additives of this invention alone or in combination with other additives can be used for blending with hydrocarbon oils or other oils in the proportions desired for the particular conditions of use to give a finished lubricating product containing the additives of this invention.

Unless otherwise stated, the percentages given herein and in the claims are percentages by weight.

Although we have described our invention by reference to specific embodiments and examples thereof, such specific embodiments and examples as have been given are merely for the purpose of illustration of the inven tion and are not intended as limiting its scope. It is in tended that modifications and variations of the present invention which are apparent from our foregoing description to those skilled in the art are to be considered within the scope of our present invention except as stated in the following appended claims.

We claim:

1. As a new composition of matter, an oil-soluble detergent neutralized reaction product prepared by the process comprising:

(1) reacting a normally liquid hydrocarbon with from about 1 percent to about 50 percent of a phosphorous sulfide at a temperature in the range from about 200 F. to about 600 F.,

(2) heating the resulting reaction product to a temperature in the range of from about 120 F. to about 400 F.,

(b) and with from about 0.1 to about 10.0 moles of the polymerization products of an unsaturated C to C fatty acid per mole of phosphorous in said reaction product, said polymerization products having a molecular weight between 300 and 2000,

(c) in the presence of an alcoholic reaction solvent selected from the class consisting of methanol, ethanol, and isopropanol, and mixtures thereof with water,

(3) partially neutralizing the resulting heated mixture at a temperature in said range with from about 0.5 to about 1.6 moles of a basic zinc compound per mole of phosphorous in said reaction product,

(4) reacting the resulting partially neutralized reaction product at a temperature in said range,

(a) with from about 1.1 to about 2.0 moles of a basic barium compound per mole of phosphorous in the reaction mixture,

(1:) and in the presence of said alcoholic reaction solvent, the alcohol of said reaction solvent being present in the reaction mixture in an amount suflicient to provide from about 2 to about 15 moles of alcohol per mole of basic barium compound,

(5) and filtering the resulting neutralized product to remove inorganic contaminants therefrom.

2. The composition of claim 1 wherein said polymerization products of an unsaturated fatty acid are polymerized products of linoleic acid consisting of from about 45 percent to about 55 percent of monomers and dimers of linoleic acid and from 45 percent to about 55 percent of trimers and higher molecular weight polymers of linoleic acid.

3. The composition of claim 1 wherein said alcoholic reaction solvent is methanol.

4. The composition of claim 1 wherein said alcoholic reaction solvent is methanol and water.

5. The composition of claim 1 wherein said alcoholic reaction solvent is isopropanol.

6. A lubricant composition comprising a major proportion of a normally liquid lubricating oil and from about 0.002 to about 15 percent of the composition of claim 1.

7. An addition agent concentrate for lubricating oils consisting essentially of a lubricating oil containing more than about 15 percent of the oil-soluble detergent neutralized reaction product of claim 1, said concentrate being capable of dilution with a normally liquid lubricating oil to a concentration of said reaction product in a range of from about 0.002 to about 15 percent.

(References on following page) 1 1 7. References Cited in the file of this patent 3,002,925 UNITED STATES PATENTS 3,003,959 2,582,958 Brennan et a1 -2 Jan. 22, 1952 2,833,713 Lemmon et a1 May 6, 1958 5 525,352 2,883,339 Richardson Apr. 21, 1959 12 Sabol et a1. Oct. 3, 1961 Wilson et a1 Oct. 10, 1961- FOREIGN PATENTS Canada May 22, 1956 Canada June 10, 1958 

1. AS A NEW COMPOSITION OF MATTER, AN OIL-SOLUBLE DETERGENT NEUTRALIZED REACTION PRODUCT PREPARED BY THE PROCESS COMPRISING: (1) REACTING A NORMALLY LIQUID HYDROCARBON WITH FROM ABOUT 1 PERCENT TO ABOUT 50 PERCENT OF A PHOSPHOROUS SULFIDE AT A TEMPERATURE IN THE RANGE FROM ABOUT 200* F. TO ABOUT 600*F., (2) HEATING THE RESULTING REACTION PRODUCT TO A TEMPERATURE IN THE RANGE OF FROM ABOUT 120*F. TO ABOUT 400*F., (A) WITH FROM ABOUT 0.5 TO ABOUT 2.5 MOLES OF BORIC ACID PER MOLE OF PHOSPHOROUS IN SAID REACTION PRODUCT, (B) AND WITH FROM ABOUT 0.1 TO ABOUT 10.0 MOLES OF THE POLYMERIZATION PRODUCTS OF AN UNSATURATED C16 TO C25 FATTY ACID PER MOLE OF PHOSPHOROUS IN SAID REACTION PRODUCT, SAID POLYMERIZATION PRODUCTS HAVING A MOLECULAR WEIGHT BETWEEN 300 AND 2000, (C) IN THE PRESENCE OF AN ALCOHOLIC REACTION SOLVENT SELECTED FROM THE CLASS CONSISTING OF METHANOL, ETHANOL, AND ISOPROPANOL, AND MIXTURES THEREOF WITH WATER, (3) PARTIALLY NEUTRALIZING THE RESULTING HEATED MIXTURE AT A TEMPERATURE IN SAID RANGE WITH FROM ABOUT 0.5 TO ABOUT 1.6 MOLES OF A BASIC ZINC COMPOUND PER MOLE OF PHOSPHOROUS IN SAID REACTION PRODUCT, (4) REACTING THE RESULTING PARTIALLY NEUTRALIZED REACTION PRODUCT AT A TEMPERATURE IN SAID RANGE, (A) WITH FROM ABOUT 1.1 TO ABOUT 2.0 MOLES OF A BASIC BARIUM COMPOUND PER MOLE OF PHOSPHOROUS IN THE REACTION MIXTURE, (B) AND IN THE PRESENCE OF SAID ALCOHOLIC REACTION SOLVENT, THE ALCOHOL OF SAID REACTION SOLVENT BEING PRESENT IN THE REACTION MIXTURE IN AN AMOUNT SUFFICIENT TO PROVIDE FROM ABOUT 2 TO ABOUT 15 MOLES OF ALCHOL PER MOLE OF BASIC BARIUM COMPOUND, (5) AND FILTERING THE RESULTING NEUTRALIZED PRODUCT TO REMOVE INORGANIC CONTAMINANTS THEREFROM. 